Prepregs for fiber composites having high strength and resilience

Abstract

The invention relates to pre-impregnating agents for high-resistant and elastic composite fibres having 50-85 mass % textile surface components and 15-50 mass % polyaminotriazine ether containing carbamide acid ester groups. The invention also relates to methods for making the pre-impregnating agents. The pre-impregnating agents can be used for heat-protecting cloths, flameproof covers, electric insulating papers, construction parts and for vehicle equipment.

1 - 11 . (canceled)  
   
   
       12 . A prepreg for fiber composites having high strength and resilience, wherein the prepreg comprises from 50 to 85% by mass of sheet-like textile structures and from 15 to 50% by mass of polyaminotriazine ethers containing carbamic ester groups and is based on 
 A) aminotriazine ethers of the structure                          wherein R 1  is —NH 2 , —NH—CHR 2 —OH, —NH—CHR 2 —O—R 3 , —NH—CHR 2 —O—R 4 —OH, —CH 3 , —C 3 H 7 , —C 6 H 5 , —OH, phthalimido, succinimido-, —NH—CO—C 5 -C 18 -alkyl, —NH—C 5 -C 18 -alkylene-OH, —NH—CHR 2 —O—C 5 -C 18 -alkylene-NH 2 , or —NH—C 5 -C 18 -alkylene-NH 2 ,    wherein R 2  is —H, or —C 1 -C 7 -alkyl,    wherein R 3  is —C 1 -C 18 -alkyl, or —R 4 —OH,    wherein R 4  is —CH(CH 3 )—CH 2 —O—C 2 -C 12 -alkylene-O—CH 2 —CH(CH 3 )—, —CH(CH 3 )—CH 2 -O—C 2 -C 12 -arylene-O—CH 2 —CH(CH 3 )—, —[CH 2 —CH 2 —O—CH 2 —CH 2 ] n —, —[CH 2 —CH(CH 3 )—O—CH 2 —CH(CH 3 )] n —, —[O—CH 2 —CH 2 —CH 2 —CH 2 ] n —, —[(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 ] n —, —[(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 ] n —, where n=1 to 200,    polyester sequences containing siloxane groups of the type [(X) r —O—CO—(Y) s —CO—O(X) r ]—, wherein X={(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 }—, {(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 }—,                          wherein r=1 to 70, s=1 to 70 and y=3 to 50,    polyether sequences which contain siloxane groups and are of the type                          wherein R 5 =H or C 1 -C 4 -alkyl and y=3 to 50,    sequences based on alkylene oxide adducts of melamine of the type comprising 2-amino-4,6-di- c2-c4 -alkyleneamino-1,3,5-triazine sequences,    phenol ether sequences based on dihydric phenols and C 2 -C 8 -diols of the type comprising —C 2 -C 8 -alkylene-O—C 6 -C 18 -arylene-O—C 2 -C 8 -alkylene sequences, and/or    B) mixtures of from 10 to 90% by mass of aminotriazine ethers A) and from 90 to 10% by mass of polyaminotriazine ethers having molar masses of from 300 to 5000, the polyaminotriazine ethers being formed by thermal autocondensation of aminotriazine ethers A), and    C) isocyanates of the formula R 6 (N═C═O) 2 , wherein R 6 =C 6 -C 14 -arylene, C 4 -C 18 -alkylene and/or C 5 -C 8 -cycloalkylene, and/or oligomeric polyesters or polyethers having terminal isocyanate groups and molar masses of from 200 to 5000,    wherein the molar ratio of triazine segment to carbamic ester groups is from 1:1 to 1:4.    
   
   
       13 . The prepreg as claimed in  claim 12 , wherein the textile substrate materials are woven fabrics or nonwovens, such as woven fabrics or nonwovens selected from the group consisting of glass fibers, carbon fibers, polyamide fibers, polyester fibers, polypropylene fibers and thermosetting plastic fibers.  
   
   
       14 . The prepreg as claimed in  claim 12 , wherein the ratio of aldehyde component to triazine component is from 1:1 to 3:1 in the polyaminotriazine ethers containing carbamic ester groups.  
   
   
       15 . The prepreg as claimed in  claim 12 , wherein the polyaminotriazine ethers containing carbamic ester groups are polyaminotriazine ethers based on at least one of melamine, formaldehyde, methanol and diisocyanates of the type R 6 (N═C═O) 2 .  
   
   
       16 . The prepreg as claimed in  claim 12 , wherein the polyaminotriazine ethers containing carbamic ester groups are polyaminotriazine ethers based on 
 B) mixtures of from 5 to 30% by mass of aminotriazine ethers A) and from 95 to 70% by mass of polyaminotriazine ethers having molar masses of from 300 to 5000, the polyaminotriazine ethers being formed by thermal autocondensation of aminotriazine ethers A), and    C) isocyanates of the formula R 6 (N═C═O) 2 , wherein R 4 =C 4 -C 18 -alkylene and/or C 5 -C 8 -cycloalkylene, and/or oligomeric polyesters or polyethers having terminal isocyanate groups and molar masses of from 200 to 5000.    
   
   
       17 . A process for the production of prepregs for fiber composites having high strength and resilience, wherein prepregs which comprise from 50 to 85% by mass of sheet-like textile structures and from 15 to 50% by mass of polyaminotriazine ethers containing carbamic ester groups are produced by a melt application method in which mixtures of 
 A) aminotriazine ethers of the structure                          wherein R 1  is —NH 2 , —NH—CHR 2 —OH, —NH—CHR 2 —O—R 3 , —NH—CHR 2 —O—R 4 —OH, —CH 3 , —C 3 H 7 , —C 6 H 5 , —OH, phthalimido, succinimido-, —NH—CO—C 5 -C 18 -alkyl, —NH—C 5 -C 18 -alkylene-OH, —NH—CHR 2 —O—C 5 -C 18 -alkylene-NH 2 , or —NH—C 5 -C 18 -alkylene-NH 2 ,    wherein R 2  is —H, or —C 1 -C 7 -alkyl,    wherein R 3  is —C 1 -C 18 -alkyl, or —R 4 —OH,    wherein R 4  is —CH(CH 3 )—CH 2 —O—C 2 -C 12 -alkylene-O—CH 2 —CH(CH 3 )—, —CH(CH 3 )—CH 2 —O—C 2 -C 12 -arylene-O—CH 2 —CH(CH 3 )—, —[CH 2 —CH 2 —O—CH 2 —CH 2 ] n —, —[CH 2 —CH(CH 3 )—O—CH 2 —CH(CH 3 )] n —, —[O—CH 2 —CH 2 —CH 2 —CH 2 ] n —, —[(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 ] n —, —[(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 ] n —, where n=1 to 200,    polyester sequences containing siloxane groups of the type [(X) r —O—CO—(Y) s —CO—O(X) r ]—, wherein    X={(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 }—, {(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 }—,                          wherein r=1 to 70, s=1 to 70 and y=3 to 50,    polyether sequences containing siloxane groups of the type                          wherein R 5 =H or C 1 -C 4 -alkyl and y=3 to 50,    sequences based on alkylene oxide adducts of melamine of the type comprising 2-amino-4,6-di-C 2 -C 4 -alkyleneamino-1,3,5-triazine sequences, or    phenol ether sequences based on dihydric phenols and C 2 -C 8 -diols of the type comprising —C 2 -C 8 -alkylene-O—C 6 -C 18 -arylene-O—C 2 -C 8 -alkylene sequences, and/or    B) mixtures of from 10 to 90% by mass of aminotriazine ethers A) and from 90 to 10% by mass of polyaminotriazine ethers having molar masses of from 300 to 5000, the polyaminotriazine ethers being formed by thermal autocondensation of aminotriazine ethers A), and    C) isocyanates of the formula R 6 (N═C═O) 2 , where R 6 =C 6 -C 14 -arylene, C 4 -C 18 -alkylene and/or C 5 -C 8 -cycloalkylene, and/or oligomeric polyesters or polyethers having terminal isocyanate groups and molar masses of from 200 to 5000,    wherein the molar ratio of diisocyanate to the sum of imino groups and amino groups in the triazine sequence is from 0.15:1 to 0.65:1, and it being possible for the mixtures to contain from 0.05 to 2% by mass, based on the aminotriazine ethers, of latent curing agents,    are melted at temperatures of from 85 to 130° C., reacted, and applied to textile substrate materials.    
   
   
       18 . A process for the production of prepregs for fiber composites having high strength and resilience, wherein prepregs having from 50 to 85% by mass of sheet-like textile structures and from 15 to 50% by mass of polyaminotriazine ethers containing carbamic ester groups are produced by a liquid application method wherein dispersions in C 5 -C 12 -hydrocarbons and/or C 3 -C 12 -ketones or solutions in dimethyl sulfoxide, dimethylformamide and/or dimethylacetamide having a solids content of from 25 to 70% by mass, comprising 
 A) aminotriazine ethers of the structure                          wherein R 1  is —NH 2 , —NH—CHR 2 —OH, —NH—CHR 2 —O—R 3 , —NH—CHR 2 —O—R 4 —OH, —CH 3 , —C 3 H 7 , —C 6 H 5 , —OH, phthalimido, succinimido-, —NH—CO—C 5 -C 18 -alkyl, —NH—C 5 -C 18 -alkylene-OH, —NH—CHR 2 —O—C 5 -C 18 -alkylene-NH 2 , or —NH—C 5 -C 18 -alkylene-NH 2 ,    wherein R 2  is —H, or —C 1 -C 7 -alkyl;    wherein R 3  is —C 1 -C 18 -alkyl, or —R 4 —OH,    wherein R 4  is —CH(CH 3 )—CH 2 —O—C 2 -C 12 -alkylene-O—CH 2 —CH(CH 3 )—, —CH(CH 3 )—CH 2 —O—C 2 -C 12 -arylene-O—CH 2 —CH(CH 3 )—, —[CH 2 —CH 2 —O—CH 2 —CH 2 ] n —, —[CH 2 —CH(CH 3 )—O—CH 2 —CH(CH 3 )] n —, —[O—CH 2 —CH 2 —CH 2 —CH 2 ] n —, —[(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 ] n —, —[(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 ] n —, where n=1 to 200,    polyester sequences containing siloxane groups of the type [(X) r —O—CO—(Y) s —CO—O(X) r ]—, wherein X={(CH 2 ) 2-8 —O—CO—C 6 -C 14 -arylene-CO—O—(CH 2 ) 2-8 }—, {(CH 2 ) 2-8 —O—CO—C 2 -C 12 -alkylene-CO—O—(CH 2 ) 2-8 }—,                          wherein r=1 to 70, s=1 to 70 and y=3 to 50,    polyether sequences containing siloxane groups and of the type                          wherein R 5 =H or C 1 -C 4 -alkyl and y=3 to 50,    sequences based on alkylene oxide adducts of melamine of the type comprising 2-amino-4,6-di-C 2 -C 4 -alkyleneamino-1,3,5-triazine sequences,    phenol ether sequences based on dihydric phenols and C 2 -C 8 -diols of the type comprising —C 2 -C 8 -alkylene-O—C 6 -C 18 -arylene-O—C 2 -C 8 -alkylene sequences, and/or    B) mixtures of from 10 to 90% by mass of aminotriazine ethers A) and from 90 to 10% by mass of polyaminotriazine ethers having molar masses of from 300 to 5000, the polyaminotriazine ethers being formed by autocondensation of triazine ethers A), and    C) isocyanates of the formula R 6 (N═C═O) 2 , wherein R 6 =C 6 -C 14 -arylene, C 4 -C 18 -alkylene and/or C 5 -C 8 -cycloalkylene, and/or oligomeric polyesters or polyethers having terminal isocyanate groups and molar masses of from 200 to 5000,    wherein the molar ratio of diisocyanate to the sum of imino groups and amino groups in the triazine sequence is from 0.15:1 to 0.65:1, and    it being possible for the mixtures to contain from 0.05 to 2% by mass, based on the aminotriazine ethers, of latent curing agents,    are applied at temperatures from 5 to 80° C. to textile substrate materials and reacted at from 80 to 120° C./from 0.1 to 1 bar and dried.    
   
   
       19 . The process for the production of prepregs as claimed in  claim 17 , wherein the aminotriazine ether used is 2,4,6-tris(methoxymethylamino)-1,3,5-triazine.  
   
   
       20 . The process for the production of prepregs as claimed in  claim 17 , wherein the latent curing agents used are weak acids, such as 
 blocked sulfonic acids,    alkali metal salts or ammonium salts of phosphoric acid,    C 1 -C 12 -alkyl esters or C 2 -C 8 -hydroxyalkyl esters of aromatic C 6 -C 14 -carboxylic acids or inorganic acids,    salts of melamine or guanamines with aliphatic C 1 -C 18 -carboxylic acids,    anhydrides, monoesters or monoamides of C 4 -C 20 -dicarboxylic acids,    monoesters or monoamides of copolymers of ethylenically unsaturated C 4 -C 20 -dicarboxylic anhydrides and ethylenically unsaturated monomers of the type comprising C 2 -C 20 -olefins and/or C 8 -C 20 -vinylaromatics, and/or    salts of C 1 -C 12 -alkylamines or alkanolamines with aliphatic C 1 -C 18 -carboxylic acids, aromatic C 6 -C 14 -carboxylic acids or alkylaromatic carboxylic acids and inorganic acids of the hydrochloric acid, sulfuric acid or phosphoric acid type.    
   
   
       21 . A fiber composite produced using prepregs as claimed in  claim 12 .  
   
   
       22 . The prepreg as claimed in  claim 13 , wherein the ratio of aldehyde component to triazine component is from 1:1 to 3:1 in the polyaminotriazine ethers containing carbamic ester groups.  
   
   
       23 . The process for the production of prepregs as claimed in  claim 18 , wherein the aminotriazine ether used is 2,4,6-tris(methoxymethylamino)-1,3,5-triazine.  
   
   
       24 . The process for the production of prepregs as claimed in  claim 18 , wherein the latent curing agents used are weak acids, such as 
 blocked sulfonic acids,    alkali metal salts or ammonium salts of phosphoric acid,    C 1 -C 12 -alkyl esters or C 2 -C 8 -hydroxyalkyl esters of aromatic C 6 -C 14 -carboxylic acids or inorganic acids,    salts of melamine or guanamines with aliphatic C 1 -C 18 -carboxylic acids,    anhydrides, monoesters or mono amides of C 4 -C 20 -dicarboxylic acids,    monoesters or monoamides of copolymers of ethylenically unsaturated C 4 -C 20 -dicarboxylic anhydrides and ethylenically unsaturated monomers of the type comprising C 2 -C 20 -olefins and/or C 8 -C 20 -vinylaromatics, and/or    salts of C 1 -C 12 -alkylamines or alkanolamines with aliphatic C 1 -C 18 -carboxylic acids, aromatic C 6 -C 14 -carboxylic acids or alkylaromatic carboxylic acids and inorganic acids of the hydrochloric acid, sulfuric acid or phosphoric acid type.    
   
   
       25 . The process for the production of prepregs as claimed in  claim 19 , wherein the latent curing agents used are weak acids, such as 
 blocked sulfonic acids,    alkali metal salts or ammonium salts of phosphoric acid,    C 1 -C 12 -alkyl esters or C 2 -C 8 -hydroxyalkyl esters of aromatic C 6 -C 14 -carboxylic acids or inorganic acids,    salts of melamine or guanamines with aliphatic C 1 -C 18 -carboxylic acids,    anhydrides, monoesters or monoamides of C 4 -C 20 -dicarboxylic acids,    monoesters or monoamides of copolymers of ethylenically unsaturated C 4 -C 20 -dicarboxylic anhydrides and ethylenically unsaturated monomers of the type comprising C 2 -C 20 -olefins and/or C 8 -C 20 -vinylaromatics, and/or    salts of C 1 -C 12 -alkylamines or alkanolamines with aliphatic C 1 -C 18 -carboxylic acids, aromatic C 6 -C 14 -carboxylic acids or alkylaromatic carboxylic acids and inorganic acids of the hydrochloric acid, sulfuric acid or phosphoric acid type.    
   
   
       26 . A fiber composite produced using prepregs as claimed in  claim 13 .  
   
   
       27 . A fiber composite produced using prepregs as claimed in  claim 14 .  
   
   
       28 . A fiber composite produced using prepregs as claimed in  claim 15 .  
   
   
       29 . A fiber composite produced using prepregs as claimed in  claim 16.